Kinetics of Isotope Exchange and Mechanisms of Catalytic Activation of Dihydrogen by Metal Complexes in Solutions Full article
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Kinetics and Catalysis
ISSN: 0023-1584 , E-ISSN: 1608-3210 |
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| Output data | Year: 1997, Volume: 38, Number: 4, Pages: 532-540 Pages count : 9 | ||
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Abstract:
Strict kinetic equations of isotope exchange of diatomic molecules were used for the first time far studying the mechanism of the catalytic activation of dihydrogen in homogeneous metal-complex systems. Theoretical bases and formal apparatus of the exchange kinetics are presented; types of exchange are classified, and approaches to the determination of their contributions from experimental data are analyzed. The kinetics of exchange of deuterium-labeled dihydrogen in homogeneous palladium phosphine complex-CF3COOH/H2O-H-2 systems was studied. It is shown that in these systems, the homoexchange of dihydrogen is absent, and two types of heteroexchange are observed, whose relative contributions vary within wide limits depending on the composition of the systems. Possible mechanisms of the catalytic activation of dihydrogen in the studied systems were analyzed on the basis of the isotope-kinetic data obtained. Taking into account the spectroscopic information on the state of the palladium complexes, we concluded that the observed regularities of exchange can be interpreted in terms of a mechanism including consecutive stages of heterolysis of dihydrogen on the Pd(II) phosphine complex and acid-type dissociation of the Pd-H bond in the palladium monohydride complex formed. It is shown that the rates of these two stages are unambiguously related to the isotope-kinetic parameters of the dihydrogen exchange.
Cite:
Muzykantov V.S.
, Zudin V.N.
, Rogov V.A.
, Shestov A.A.
, Likholobov V.A.
Kinetics of Isotope Exchange and Mechanisms of Catalytic Activation of Dihydrogen by Metal Complexes in Solutions
Kinetics and Catalysis. 1997. V.38. N4. P.532-540. WOS Scopus РИНЦ ANCAN
Kinetics of Isotope Exchange and Mechanisms of Catalytic Activation of Dihydrogen by Metal Complexes in Solutions
Kinetics and Catalysis. 1997. V.38. N4. P.532-540. WOS Scopus РИНЦ ANCAN
Original:
Музыкантов В.С.
, Зудин В.Н.
, Рогов В.А.
, Шестов А.А.
, Лихолобов В.А.
Изотопная кинетика обмена и механизмы каталитической активации диводорода комплексами металлов в растворах
Кинетика и катализ. 1997. Т.38. №4. С.581-590. РИНЦ
Изотопная кинетика обмена и механизмы каталитической активации диводорода комплексами металлов в растворах
Кинетика и катализ. 1997. Т.38. №4. С.581-590. РИНЦ
Dates:
| Submitted: | Mar 11, 1996 |
Identifiers:
| Web of science: | WOS:A1997XU99700015 |
| Scopus: | 2-s2.0-0642305130 |
| Elibrary: | 13263138 |
| Chemical Abstracts: | 1997:597179 |
| Chemical Abstracts (print): | 127:196081 |